Polyelectrolyte dental adhesives for whitening teeth and teeth components

ABSTRACT

This document relates to methods and materials involved in providing a tooth, tooth component, or inorganic dental material (e.g., a human tooth, a human tooth component, or an inorganic dental material within a human&#39;s mouth) with a white appearance. For example, a whitening adhesive containing a conjugate of at least a polyamine, a polyphosphate, and one or more whitening agents (e.g., titanium dioxide, zinc oxide, and/or hydroxyapetite) can be used to provide a tooth, tooth component, or inorganic dental material with a whiter appearance.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.16/236,056, filed Dec. 28, 2018, which is a continuation of U.S.application Ser. No. 15/920,154, filed Mar. 13, 2018 (now U.S. Pat. No.10,201,491), which is a continuation of U.S. application Ser. No.15/473,355, filed Mar. 29, 2017 (now U.S. Pat. No. 9,937,120), whichclaims the benefit of U.S. Provisional Application Ser. No. 62/314,798,filed Mar. 29, 2016. The disclosure of the prior applications areconsidered part of (and are incorporated by reference in) the disclosureof this application.

BACKGROUND 1. Technical Field

This document relates to methods and materials involved in providing atooth, tooth component, or inorganic dental material (e.g., a humantooth, a human tooth component, or an inorganic dental material within ahuman's mouth) with a white appearance. For example, the documentrelates to methods and materials for contacting a tooth, toothcomponent, or inorganic dental material with a whitening adhesive (e.g.,a polyelectrolyte whitening adhesive) containing a conjugate of at leasta polyamine, a polyphosphate, and one or more whitening agents (e.g.,titanium dioxide and/or hydroxyapatite) to provide teeth with a whiterappearance.

2. Background Information

White teeth are considered cosmetically desirable. However, teeth canbecome discolored in the absence of intervention. The tooth structurethat is generally responsible for presenting a stained appearance is theenamel layer. Several factors can contribute to enamel discoloration.For example, the formation of plaque and tartar matrices on the toothsurface can entrap stains, thereby leading to enamel discoloration.

Over-the-counter tooth whitening preparations have been developed toaddress the cosmetic preference of many to restore luster to toothenamel discolored by surface entrapped materials. While all dentifricesand mouthwashes contain some cleaning and polishing agents, some enameldeposits become intractable to being fully removed by these agents undernormal use conditions. Smokers often develop discolored enamel becausethe tars and particulates in cigarette smoke collect on the teeth. Insome case, foods and drinks (e.g., tea) and/or antibiotics (e.g.,tetracycline) can stain or discolor tooth enamel.

SUMMARY

This document provides methods and materials for contacting a tooth,tooth component, or inorganic dental material (e.g., a human tooth, ahuman tooth component, or an inorganic dental material within a human'smouth) with a whitening adhesive (e.g., a polyelectrolyte whiteningadhesive) containing a conjugate of at least a polyamine, apolyphosphate, and one or more whitening agents (e.g., titanium dioxide(TiO₂) and/or hydroxyapatite (HA)) to provide the tooth, toothcomponent, or inorganic dental material with a whiter appearance. Forexample, a whitening adhesive containing a conjugate of at least apolyamine, a polyphosphate, and a whitening agent (e.g., TiO₂ and/or HA)can be used to provide teeth with a whiter appearance. In some cases, awhitening adhesive provided herein can be applied to a surface of atooth, tooth component, or inorganic dental material. In some cases, apolyamine, a polyphosphate, and one or more whitening agents can beapplied to a tooth, tooth component, or inorganic dental material, and awhitening adhesive can be formed on a surface of the tooth, toothcomponent, or inorganic dental material. The methods and materialsprovided herein can allow a person to have white appearing teeth eventhough the teeth may be stained. In some cases, white appearing teethcan be obtained using the methods and materials provided herein withoutharsh bleaching or de-staining techniques.

In general, one aspect of this document features a whitening adhesive.The whitening adhesive contains, or consists essentially of, a conjugateof a polyamine, a polyphosphate, and a whitening agent. The whiteningagent has the ability to interact with or bind to a tooth, a toothcomponent, or an inorganic dental material. The whitening agent of thewhitening adhesive provides teeth with a white appearance when thewhitening adhesive is adhered to a tooth, a tooth component, or aninorganic dental material. The polyamine can be polyallylamine, PAS-92,PAA-D41, polylysine, or polyethyleneimine. The polyphosphate can besodium hexametaphosphate, sodium trimetaphosphate, sodiumtripolyphosphate, or sodium pyrophosphate. The whitening adhesive canhave a w/w ratio of polyamine to polyphosphate of about 1:1 to about1:20 (e.g., about 1:6.7). The whitening agent can include at least oneof TiO₂, HA, silicon dioxide, zinc oxide (ZnO), bioactive glass, andblue fluorescent protein. The whitening agent can be TiO₂, where theTiO₂ comprises from about 0.05 wt % to about 2 wt % of the whiteningadhesive. The whitening agent can be ZnO, where the ZnO comprises fromabout 0.5 wt % to about 10 wt % of the whitening adhesive. The whiteningagent also can include HA, where the HA comprises from about 1 wt % toabout 20 wt % of the whitening adhesive. The whitening agent also caninclude blue fluorescent protein.

In another aspect, this document features a method for altering anappearance of teeth. The method can include, or consist essentially or,applying to teeth a polyamine, a polyphosphate, and a whitening agent toform a whitening adhesive on a surface of said teeth, such that thewhitening agent of the whitening adhesive can alter said appearance ofthe teeth. The teeth can be human teeth. The method can include alteringthe appearance of the teeth such that the teeth appear whiter. Thepolyamine can be polyallylamine, PAS-92, PAA-D41, polylysine, orpolyethyleneimine. The polyphosphate can be sodium hexametaphosphate,sodium trimetaphosphate, sodium tripolyphosphate, or sodiumpyrophosphate. The whitening adhesive can have a w/w ratio of polyamineto polyphosphate of about 1:1 to about 1:20 (e.g., about 1:6.7). Thewhitening agent can include at least one of TiO₂, HA, silicon dioxide,ZnO, bioactive glass, and blue fluorescent protein. The whitening agentcan be TiO₂, where the TiO₂ comprises from about 0.05 wt % to about 2 wt% of the whitening adhesive. The whitening agent can be ZnO, where theZnO comprises from about 0.5 wt % to about 10 wt % of the whiteningadhesive. The whitening agent also can include HA, and where the HAcomprises from about 1 wt % to about 20 wt % of the whitening adhesive.The whitening agent also can include blue fluorescent protein.Fluorescence emitted from the blue fluorescent protein can alter theappearance of said teeth such that said teeth appear whiter. Theapplying step can occur in the presence of saliva.

In another aspect, this document features a toothpaste. The toothpastecan include a polyamine, a polyphosphate, and a whitening agent, suchthat the polyamine, the polyphosphate, and the whitening agent form awhitening adhesive on a surface of a tooth, a tooth component, or aninorganic dental material when said toothpaste is applied to the tooth,the tooth component, or the inorganic dental material. The whiteningagent of the whitening adhesive can alter the appearance of said tooth,said tooth component, or said inorganic dental material. The whiteningadhesive can include from about 1 wt % to about 10 wt % polyamine.

In another aspect, this document features a mouth rinse. The mouth rinsecan include a polyamine, a polyphosphate, and a whitening agent, suchthat the polyamine, the polyphosphate, and the whitening agent form awhitening adhesive on a surface of a tooth, a tooth component, or aninorganic dental material when the mouth rinse is applied to the tooth,the tooth component, or the inorganic dental material. The whiteningagent of the whitening adhesive can alter the appearance of said tooth,said tooth component, or said inorganic dental material. The whiteningadhesive can include from about 0.1 wt % to about 1 wt % polyamine.

In another aspect, this document features a kit. The kit can include afirst composition comprising a polyamine and a whitening agent and asecond composition comprising a polyphosphate. Contacting the firstcomposition with the second composition can form a whitening adhesiveincluding, or consisting essentially of, a conjugate of thepolyphosphate, the polyamine, and the whitening agent. The whiteningagent of the whitening adhesive can alter an appearance of a tooth, atooth component, or an inorganic dental material when the whiteningadhesive is applied to the tooth, the tooth component, or the inorganicdental material.

In another aspect, this document features a method for altering anappearance of a tooth, tooth component, or inorganic dental material.The method can include applying a polyamine and a whitening agent to thetooth, tooth component, or inorganic dental material, and applying apolyphosphate to the tooth, tooth component, or inorganic dentalmaterial such that the polyphosphate, the polyamine, and the whiteningagent form a whitening adhesive on a surface of the tooth, toothcomponent, or inorganic dental material when applied to the tooth, toothcomponent, or inorganic dental material. The whitening agent of thewhitening adhesive can alter the appearance of the tooth, toothcomponent, or inorganic dental material.

In another aspect, this document features a method for altering anappearance of a tooth, tooth component, or inorganic dental material.The method can include applying to teeth a conjugate including, orconsisting essentially of, at least a polyamine, a polyphosphate, and awhitening agent, to form a coating on a surface of the teeth. Thecoating can alter the appearance of the teeth. The teeth can be humanteeth. The method can alter the appearance of the teeth such that theteeth appear whiter. The polyamine can be polyallylamine, PAS-92,PAA-D41, polylysine, or polyethyleneimine. The polyphosphate can besodium hexametaphosphate, sodium trimetaphosphate, sodiumtripolyphosphate, or sodium pyrophosphate. The coating can include a w/wratio of polyamine to polyphosphate of about 1:1 to about 1:20 (e.g.,about 1:6.7). The whitening agent can include at least one of TiO₂, HA,silicon dioxide, ZnO, and blue fluorescent protein. The whitening agentcan be TiO₂, where the TiO₂ comprises from about 0.05 wt % to about 2 wt% of the whitening adhesive. The whitening agent can be ZnO, where theZnO comprises from about 0.5 wt % to about 10 wt % of the whiteningadhesive. The whitening agent also can include HA, where the HAcomprises from about 1 wt % to about 20 wt % of the whitening adhesive.The whitening agent also can include blue fluorescent protein.Fluorescence emitted from the blue fluorescent protein can alter theappearance of the teeth such that the teeth appear whiter. The applyingstep can occur in the presence of saliva.

In another aspect, this document features a whitening adhesivecomprising, or consisting essentially of, a conjugate of a polyamine, apolyphosphate, and a whitening agent and having the ability to interactwith or bind to a tooth, a tooth component, or an inorganic dentalmaterial. The whitening agent of the whitening adhesive provides teethwith a white appearance when the whitening adhesive is adhered to thetooth, the tooth component, or the inorganic dental material, whereinthe polyamine comprises from about 5 wt % to about 15 wt % of thewhitening adhesive, wherein the polyphosphate comprises from about 25 wt% to about 35 wt % of the whitening adhesive, and wherein the whiteningagent comprises from about 10 wt % to about 20 wt % of the whiteningadhesive. The polyamine can be selected from the group consisting ofpolyallylamine, PAS-92, PAA-D41, polylysine, and polyethyleneimine. Thepolyphosphate can be selected from the group consisting of sodiumhexametaphosphate, sodium trimetaphosphate, sodium tripolyphosphate, andsodium pyrophosphate. The whitening agent can comprise at least one oftitanium dioxide, hydroxyapatite, silicon dioxide, zinc oxide, and bluefluorescent protein. The polyamine can be PAA-D41, the polyphosphate canbe sodium trimetaphosphate, and the whitening agent can be zinc oxide.The polyamine can be polyallylamine, the polyphosphate can be sodiumtrimetaphosphate, and the whitening agent can be zinc oxide.

In another aspect, this document features a method for altering anappearance of teeth. The method comprises, or consists essentially of,applying to teeth a whitening adhesive comprising, or consistingessentially of, a conjugate of a polyamine, a polyphosphate, and awhitening agent and having the ability to interact with or bind to atooth, a tooth component, or an inorganic dental material. The whiteningagent of the whitening adhesive provides teeth with a white appearancewhen the whitening adhesive is adhered to the tooth, the toothcomponent, or the inorganic dental material, wherein the polyaminecomprises from about 5 wt % to about 15 wt % of the whitening adhesive,wherein the polyphosphate comprises from about 25 wt % to about 35 wt %of the whitening adhesive, and wherein the whitening agent comprisesfrom about 10 wt % to about 20 wt % of the whitening adhesive. Thepolyamine can be selected from the group consisting of polyallylamine,PAS-92, PAA-D41, polylysine, and polyethyleneimine. The polyphosphatecan be selected from the group consisting of sodium hexametaphosphate,sodium trimetaphosphate, sodium tripolyphosphate, and sodiumpyrophosphate. The whitening agent can comprise at least one of titaniumdioxide, hydroxyapatite, silicon dioxide, zinc oxide, and bluefluorescent protein. The polyamine can be PAA-D41, the polyphosphate canbe sodium trimetaphosphate, and the whitening agent can be zinc oxide.The polyamine can be polyallylamine, the polyphosphate can be sodiumtrimetaphosphate, and the whitening agent can be zinc oxide.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this disclosure pertains. Methods and materials aredescribed herein for use in the present disclosure; other, suitablemethods and materials known in the art can also be used. The materials,methods, and examples are illustrative only and not intended to belimiting. All publications, patent applications, patents, sequences,database entries, and other references mentioned herein are incorporatedby reference in their entirety. In case of conflict, the presentspecification, including definitions, will control.

The details of one or more embodiments of the invention are set forth inthe accompanying drawings and the description below. Other features,objects, and advantages of the invention will be apparent from thedescription and drawings, and from the claims.

DESCRIPTION OF DRAWINGS

FIG. 1 shows examples of polyamines: polyallylamine (PAA), a co-polymerof secondary amine and sulfur dioxide (PAS-92), and a copolymer ofprimary amine and secondary amine (PAA-D41-HCl).

FIG. 2 shows examples of polyphosphates: sodium pyrophosphate (PP),sodium tripolyphosphate (TPP), sodium trimetaphosphate (STP), and sodiumhexametaphosphate (SHMP).

FIGS. 3A and 3B are schematic diagrams of exemplary procedures for thepreparation of a whitening adhesive. FIG. 3A shows preparation of adilute whitening adhesive in large volumes. FIG. 3B shows preparation ofa concentrated whitening adhesive in small volumes.

FIG. 4 contains photographs showing the appearance of whiter teethfollowing application of an exemplary whitening adhesive containing aconjugate of PAA, STP, and TiO₂ (top panel) or a conjugate of PAS-92,STP, and TiO₂ (bottom panel), as described in exemplary procedure FIG.3A.

FIG. 5 contains photographs showing the appearance of whiter teethfollowing application of an exemplary whitening adhesive containing aconjugate of PAA, STP, and TiO₂, as described in exemplary procedureFIG. 3B.

FIG. 6 contains photographs showing the appearance of whiter teethfollowing application of an exemplary whitening adhesive containing aconjugate of PAA, STP, and TiO₂, and hydroxyapatite (HA) either alone oras a part of the conjugate.

FIG. 7 contains photographs showing the appearance of whiter teethfollowing application of an exemplary whitening adhesive containing aconjugate of PAA, STP, and TiO₂ and blue fluorescent protein (BFP),either alone or as part of the conjugate.

FIG. 8 contains photographs showing the appearance of whiter teethfollowing application of an exemplary whitening adhesive containing aconjugate of PAA, STP, and TiO₂ and ZnO (top panel) or an exemplarywhitening adhesive containing a conjugate of PAA, STP, and ZnO (bottompanel).

FIGS. 9A and 9B contain photographs showing the appearance of whiterteeth following application of an exemplary whitening adhesivecontaining a conjugate of a polyamine, a polyphosphate, and a whiteningagent. FIG. 9A contains photographs showing the appearance of whiterteeth following application of an exemplary whitening adhesivecontaining a conjugate of PAA, various polyphosphates (STP, SHMP, PP,and TPP), and TiO₂. FIG. 9B contains photographs showing the appearanceof whiter teeth following application of an exemplary whitening adhesivecontaining a conjugate of PAS-92, various polyphosphates (STP, SHMP, PP,and TPP), and TiO₂.

DETAILED DESCRIPTION

This document provides methods and materials for using a whiteningadhesive (e.g., a polyelectrolyte whitening adhesive) containing aconjugate of at least a polyamine, a polyphosphate, and one or morewhitening agents (e.g., TiO₂, ZnO, and/or HA) to adhere to a tooth, atooth component, or an inorganic dental material (e.g., a human tooth, ahuman tooth component, or an inorganic dental material within a human'smouth). For example, this document provides methods and materials foradhering or attaching a whitening agent to teeth as a coating to providea whiter appearance. In some cases, this document provides methods andmaterials for contacting teeth with a whitening adhesive containing aconjugate of at least a polyamine, a polyphosphate, and one or morewhitening agents to provide the teeth with a coating that provides awhiter appearance that can be maintained after brushing.

A whitening adhesive containing a conjugate of at least a polyamine, apolyphosphate, and one or more whitening agents (e.g., TiO₂, ZnO, and/orHA) can be a polyelectrolyte adhesive and can have the ability tointeract with or bind to a tooth, a tooth component (e.g., enamel,hydroxyapatite, acquired dental pellicle, cementum, crown, cervix,cementoenamel junction, or apex), or inorganic dental materials (e.g.,crowns, caps, braces, or fillings) using weak or strong ionic orcovalent interactions to the surface of the tooth, tooth component, orinorganic dental material, thus attaching or adhering a whitening agentto the tooth, tooth component, or inorganic dental material. A whiteningadhesive (e.g., a polyelectrolyte whitening adhesive) can adhere toorganic or inorganic materials on the surface of a tooth, toothcomponent, or inorganic dental material. A tooth, tooth component, orinorganic dental material can be from a mammal (e.g., a human, dog, cat,cow, or horse).

A whitening adhesive (e.g., a polyelectrolyte whitening adhesive) can beformed by contacting a polycation, a polyanion, and one or morewhitening agents (e.g., TiO₂, ZnO, and/or HA). For example, a whiteningadhesive can be formed by contacting a polyamine, a polyphosphate, andone or more whitening agents. When forming a whitening adhesivedescribed herein, the polyamine, the polyphosphate, and the one or morewhitening agents can be provided separately, together, or in anycombination. In cases where a polyamine, a polyphosphate, and one ormore whitening agents are provided separately, they can be providedsimultaneously or serially. A polyamine, a polyphosphate, and one ormore whitening agents provided serially can be provided in any order. Insome cases, a whitening adhesive provided herein can be formed bycontacting a first composition containing a polyphosphate (e.g., STP) toa second composition containing a polyamine (e.g., PAA) and a whiteningagent (e.g., TiO₂). In some cases, a whitening adhesive provided hereincan be formed by contacting a first composition containing apolyphosphate (e.g., STP) and one or more whitening agents to a secondcomposition containing a polyamine (e.g., PAA). When forming a whiteningadhesive described herein, the polyamine, the polyphosphate, and the oneor more whitening agents can be provided in any form (e.g., a solution,powder, gel, or suspension). In some cases, a whitening adhesiveprovided herein can be formed by contacting a powder form of apolyphosphate (e.g., STP) to a solution containing a polyamine (e.g.,PAA) and one or more whitening agents (e.g., TiO₂, ZnO, and/or HA).

Any appropriate polyamine can be used to form a whitening adhesivedescribed herein. A polyamine can be a polymer containing repeatingunits of primary amines, secondary amines, amines mixed with otherrepeat units (e.g., such as sulfur dioxide), or combinations thereof.Examples of a polyamines that can be used to form a whitening adhesivedescribed herein include, without limitation, PAA, copolymers of aprimary and secondary amine (e.g. PAA-D41-HCl), copolymers of secondaryamine and sulfur dioxide (e.g., PAS-92), PAA hydrochloride,polydiallylamine (DAA), polyampholite, chitosan, polylysine, polyvinylamine, polyethyleneimine (PEI), heparin, and EUDRAGIT® E 100. Apolyamine polymer described herein can be a hydrochloride salt form or afree base form. Additional examples of polyamines that can be used toform a whitening adhesive described herein include, without limitation,those commercially available from Nittobo Medical Co., LTD (see, e.g.,the PAS series, the PAA series, and the polyampholite series). Apolyamine used to form a whitening adhesive described herein can be ahomopolymer, copolymer, or a combination thereof. In some cases, apolyamine used as described herein can have a molecular weight of lessthan about 200,000 (e.g., less than about 100,000; less than about50,000; less than about 30,000; less than about 15,000; or less thanabout 10,000). For example, a polyamine used as described herein canhave a molecular weight of about 5,000 to about 20,000. In some cases, apolyamine used as described herein can have a pH of about 6 to about 10(e.g., about 6.5 to about 9, about 7 to about 9.5, or about 8 to about9). A polyamine can be pH adjusted to have a pH of about 6 to about 10.

A whitening adhesive containing a conjugate of at least a polyamine, apolyphosphate, and one or more whitening agents described herein caninclude from about 0.1 weight percent to about 10 weight percent of thepolyamine (e.g., PAA, PAA-D41-HCl, PAS-92, PEI, or polylysine). In somecases, a dilute whitening adhesive can be used, for example, as a mouthrinse, and can include about 0.1 wt % to about 1 wt % (e.g., from about0.2 wt % to about 0.9 wt %, from about 0.3 wt % to about 0.8 wt %, fromabout 0.4 wt % to about 0.7 wt %, or from about 0.5 wt % to about 0.6 wt%) polyamine. In some cases, a concentrated whitening adhesive can beused, for example, as a toothpaste or gel, and can include about 1 wt %to about 10 wt % (e.g., from about 2 wt % to about 9 wt %, from about 3wt % to about 8 wt %, from about 4 wt % to about 7 wt %, from about orfrom about 5 wt % to about 6 wt %) polyamine.

Any appropriate polyphosphate can be used to form a whitening adhesivedescribed herein. A polyphosphate can be a cyclic polyphosphate, alinear polyphosphate, a potassium salt of a polyphosphate, or a sodiumphosphate salt of a polyphosphate. A polyphosphate can be a polymerhaving any phosphate-containing compound or salt thereof. Examples ofpolyphosphates that can be used as described herein include, withoutlimitation, hexametaphosphate (e.g., SHMP), trimetaphosphate (e.g.,STP), tripolyphosphate (e.g., TPP), pyrophosphate (e.g., PP).Optionally, other poly-acids can also be introduced such as alginates(e.g., alginic acid), crosslinked with CaCl₂), carrageenan,polylactic-co-glycolic acid (PLGA), polyacrylic acid,polystyrenesulfate, polyvinyl sulfate, polyglutamic acid, and/orpolyaspartic acid. A polyphosphate used to form a whitening adhesivedescribed herein can be a homopolymer, copolymer, or a combinationthereof. In some cases, a polyphosphate used as described herein canhave a molecular weight greater less than about 50,000 (e.g., less thanabout 20,000; less than about 5,000; less than about 3,000; less thanabout 2,000; or less than about 1,000). In some cases, a polyphosphatecan aid in enamel remineralization.

A whitening adhesive containing a conjugate of at least a polyamine, apolyphosphate, and one or more whitening agents described herein caninclude from about 0.05 wt % to about 25 wt % of polyphosphate (e.g.,STP, SHMP, TPP, or PP). In some cases, a dilute whitening adhesive canbe used, for example, as a mouth rinse, and can include about 0.05 wt %to about 1 wt % (e.g., from about 0.1 wt % to about 0.9 wt %, from about0.15 wt % to about 0.8 wt %, from about 0.2 wt % to about 0.7 wt %, orfrom about 0.25 wt % to about 0.6 wt %) polyphosphate. In some cases, aconcentrated whitening adhesive can be used, for example, as atoothpaste or gel, and can include about 1 wt % to about 25 wt % (e.g.,from about 2 wt % to about 20 wt %, from about 3 wt % to about 15 wt %,from about 4 wt % to about 10 wt %, or from about 5 wt % to about 8 wt%) polyphosphate. In some cases, the wt % of the polyphosphate can becomparable to the wt % of the polyamine. In some cases, the wt % of thepolyphosphate can be higher (e.g., 2 times (2×) higher, 3× higher, 5×higher, 7× higher, 10× higher, or 20× higher) than the wt % of thepolyamine.

In some cases, a whitening adhesive containing a conjugate of at least apolyamine, a polyphosphate, and one or more whitening agents describedherein can include a w/w ratio of polyamine (e.g., PAA, PAA-D41-HCl,PAS-92, PEI, and/or polylysine) to polyphosphate (e.g., STP, SHMP, TPP,and/or PP) of about 5:1 to about 1:20 (e.g., about 2:1 to about 1:18,about 1:1 to about 1:15, about 1:1 to about 1:12, about 1:1 to about1:10, about 1:2 to about 1:9, about 1:3 to about 1:8, or about 1:5 toabout 1:8). For example, a whitening adhesive described herein caninclude a w/w ratio of polyamine to polyphosphate of about 1:6.7. Insome cases, a whitening adhesive containing a conjugate of at least apolyamine, a polyphosphate, and one or more whitening agents describedherein can include a w/w ratio of polyamine (e.g., PAA, PAA-D41-HCl,PAS-92, PEI, and/or polylysine) to polyphosphate (e.g., STP, SHMP, TPP,and/or PP) of about 10:1 to about 1:10.

Any appropriate method can be used to make a whitening adhesivecontaining a conjugate of at least a polyamine, a polyphosphate, and oneor more whitening agents described herein, and having the ability tointeract with and/or bind to tooth, tooth component, or inorganic dentalmaterial. In some cases, a polyamine and/or a polyphosphate can beobtained from a commercial source or can be synthesized from thepolymerization of a desired monomer or combination of differentmonomers. In some cases, standard polymer synthesis techniques (e.g.,addition polymerization, sol-gel synthesis, phase separation,template-assisted synthesis, step growth polymerization, orco-polymerization using chemical or photochemical radical synthesis) canbe used to produce polyamines and/or polyphosphates.

Any appropriate whitening agent can be used to form a whitening adhesivedescribed herein. Examples of whitening agents that can be used in awhitening adhesive described herein include, without limitation,particles composed of TiO₂, ZnO, HA, silicon dioxide (SiO₂), bioactiveglass, zirconium silicate, and/or calcium phosphate. See, e.g.,Schilling et al., Photochem. Photobiol. Sci., 9:495-509 (2010); and U.S.Pat. No. 6,004,567. Particulate whitening agents can range in size fromabout 5 nanometer (nm) to about 1000 nm (1 m) in size (e.g., from about10 nm to about 900 nm, from about 25 nm to about 750 nm, from about 50nm to about 500 nm, from about 75 nm to about 450 nm, from about 100 nmto about 400 nm, from about 125 nm to about 350 nm, or from about 150 nmto about 300 nm).

In some cases, BFP can be used as a whitening agent to make a whiteningadhesive provided herein. See, e.g., U.S. Pat. Nos. 8,568,698; and8,784,783. For example, a polypeptide that emits blue fluorescence canbe combined with a polyamine and a polyphosphate to form a whiteningadhesive described herein for coating teeth to provide a whiterappearance. A BFP can have an emission wavelength from about 400 nm toabout 500 nm (e.g., from about 410 nm to about 500 nm, from about 420 nmto about 500 nm, from about 430 nm to about 500 nm, from about 440 nm toabout 500 nm, from about 440 nm to about 490 nm, from about 440 nm toabout 480 nm, from about 440 nm to about 470 nm, from about 440 nm toabout 460 nm, from about 450 nm to about 490 nm, or from about 460 nm toabout 480 nm). In some cases, a fluorescent polypeptide that emitsfluorescence at an emission wavelength of from about 490 nm to about 600nm (e.g., from about 430 nm to about 450 nm, from about 440 nm to about450 nm, from about 420 nm to about 440 nm, or from about 485 nm to about505 nm) can be used as a whitening agent to make a composition providedherein, and can be applied to teeth as described herein.

In some cases, a whitening adhesive containing a conjugate of at least apolyamine, a polyphosphate, and one or more whitening agents describedherein can include two or more whitening agents (e.g., two whiteningagents, three whitening agents, four whitening agents, or five whiteningagents). For example, a whitening adhesive can include TiO₂ and HA; TiO₂and BFP; HA and BFP; TiO₂, HA and BFP; TiO₂ and ZnO; TiO₂ and SiO₂; HAand SiO₂; or TiO₂, HA, SiO₂, ZnO and BFP. A whitening agent can becovalently or non-covalently attached to any component of a whiteningadhesive such as a polyamine and/or a polyphosphate.

A whitening adhesive containing a conjugate of at least a polyamine, apolyphosphate, and one or more whitening agents described herein caninclude from about 0.05 weight percent to about 20 weight percentwhitening agent. For example, a whitening adhesive described herein caninclude from about 0.05 weight percent to about 2 weight percent (e.g.,from about 0.07 wt % to about 1.9 wt %, from about 0.09 wt % to about1.8 wt %, or from about 1 wt % to about 1.5 wt %) TiO₂. For example, awhitening adhesive described herein can include from about 0.5 wt % toabout 10 wt % (e.g., from about 0.7 wt % to about 9 wt %, from about 0.9wt % to about 8 wt %, or from about 1 wt % to about 7 wt %) ZnO. Forexample, a whitening adhesive described herein can include from about 1wt % to about 20 wt % (e.g., from about 2 wt % to about 19 wt %, fromabout 3 wt % to about 18 wt %, from about 4 wt % to about 17 wt %, orfrom about 5 wt % to about 15 wt %) HA.

In some cases, a whitening adhesive containing a conjugate of one ormore polyamines, one or more polyphosphates, and one or more whiteningagents described herein can include from about 0.1 wt % to about 15 wt %(e.g., from about 3.5 wt % to about 15 wt %, from about 5 wt % to about15 wt %, from about 7 wt % to about 15 wt %, from about 3.5 wt % toabout 11 wt %, from about 3.5 wt % to about 10 wt %, from about 5 wt %to about 12 wt %, from about 6 wt % to about 8 wt %, or from about 9 wt% to about 11 wt %) of polyamine(s), from about 0.05 wt % to about 60 wt% (e.g., from about 1 wt % to about 60 wt %, from about 5 wt % to about60 wt %, from about 10 wt % to about 60 wt %, from about 20 wt % toabout 60 wt %, from about 25 wt % to about 60 wt %, from about 5 wt % toabout 50 wt %, from about 5 wt % to about 40 wt %, from about 20 wt % toabout 40 wt %, from about 25 wt % to about 35 wt %, from about 7.5 wt %to about 15 wt %, or from about 9 wt % to about 12 wt %) ofpolyphosphate(s), and from about 0.05 wt % to about 45 wt % (e.g., fromabout 5 wt % to about 45 wt %, from about 5 wt % to about 40 wt %, fromabout 5 wt % to about 35 wt %, from about 5 wt % to about 30 wt %, fromabout 10 wt % to about 45 wt %, from about 15 wt % to about 45 wt %,from about 20 wt % to about 45 wt %, from about 10 wt % to about 20 wt%, from about 12 wt % to about 17 wt %, from about 20 wt % to about 40wt %, from about 25 wt % to about 35 wt %, from about 28 wt % to about33 wt %, from about 30 wt % to about 45 wt %, or from about 35 wt % toabout 40 wt %) of whitening agent(s). In some cases, a whiteningadhesive containing a conjugate of one or more polyamines, one or morepolyphosphates, and one or more whitening agents described herein caninclude from about 5 wt % to about 15 wt % of a polyamine such asPAA-D41, from about 25 wt % to about 35 wt % of a polyphosphate such asSTP, and from about 10 wt % to about 20 wt % of a whitening agent suchas ZnO. In some cases, a whitening adhesive containing a conjugate ofone or more polyamines, one or more polyphosphates, and one or morewhitening agents described herein can include from about 5 wt % to about15 wt % of a polyamine such as PAA, from about 25 wt % to about 35 wt %of a polyphosphate such as STP, from about 10 wt % to about 20 wt % of awhitening agent such as ZnO, and from about 0.1 wt % to about 5 wt % ofa whitening agent such as TiO₂. In some cases, a whitening adhesivecontaining a conjugate of one or more polyamines, one or morepolyphosphates, and one or more whitening agents described herein caninclude from about 5 wt % to about 15 wt % of a polyamine such asPAA-D41, from about 25 wt % to about 35 wt % of a polyphosphate such asTPP, and from about 10 wt % to about 20 wt % of a whitening agent suchas ZnO. In some cases, a whitening adhesive containing a conjugate ofone or more polyamines, one or more polyphosphates, and one or morewhitening agents described herein can include from about 5 wt % to about15 wt % of a polyamine such as PAA-D41, from about 25 wt % to about 35wt % of a polyphosphate such as TPP, and from about 1 wt % to about 10wt % of a whitening agent such as ZnO. In some cases, a whiteningadhesive containing a conjugate of one or more polyamines, one or morepolyphosphates, and one or more whitening agents described herein caninclude from about 5 wt % to about 15 wt % of a polyamine such as PAA,from about 25 wt % to about 35 wt % of a polyphosphate such as STP, fromabout 20 wt % to about 30 wt % of a whitening agent such as ZnO, andfrom about 0.1 wt % to about 5 wt % of a whitening agent such as TiO₂.In some cases, a whitening adhesive containing a conjugate of one ormore polyamines, one or more polyphosphates, and one or more whiteningagents described herein can include from about 1 wt % to about 10 wt %of a polyamine such as PAA, from about 5 wt % to about 15 wt % of apolyphosphate such as STP, from about 5 wt % to about 20 wt % of awhitening agent such as ZnO, and optionally from about 0.1 wt % to about5 wt % of a whitening agent such as TiO₂. In some cases, a whiteningadhesive containing a conjugate of one or more polyamines, one or morepolyphosphates, and one or more whitening agents described herein caninclude from about 5 wt % to about 15 wt % of a polyamine such as PAA,from about 25 wt % to about 35 wt % of a polyphosphate such as STP, andfrom about 10 wt % to about 20 wt % of a whitening agent such as ZnO.

A whitening adhesive containing a conjugate of at least a polyamine, apolyphosphate, and one or more whitening agents described herein alsocan contain one or more other molecules. For example, a whiteningadhesive also can be combined with a therapeutic agent (e.g. fluorideand/or antibacterial compounds), remineralization particles (e.g., HA,fluoride, calcium, magnesium, phosphate, iron, and/or tin ions, and anysalt forms thereof), astringent salts, odor neutralizers,anti-gingivitis agents, anti-plaque agents, anti-tartar agents, or anycombination thereof.

This document also provides methods for applying a whitening adhesivecontaining a conjugate of at least a polyamine, a polyphosphate, and oneor more whitening agents described herein. In some cases, a whiteningadhesive can be formed and then applied directly to a tooth, toothcomponent, or inorganic dental material in a single step. In some cases,a polyamine, a polyphosphate, and one or more whitening agents can beapplied to a tooth, tooth component, or inorganic dental material inseparate steps and a whitening adhesive can be formed on the tooth,tooth component, or inorganic dental material. In cases where apolyamine, a polyphosphate, and one or more whitening agents are appliedseparately, the application can be simultaneous or non-simultaneous. Forexample, a polyamine, a polyphosphate, and one or more whitening agentscan be applied to a tooth, tooth component, or inorganic dental materialsimultaneously using a multi-channel delivery applicator (e.g., a dualchannel delivery applicator). For example, a polyamine, a polyphosphate,and one or more whitening agents can be applied non-simultaneously to atooth, tooth component, or inorganic dental material using a firstcomposition (e.g., containing a polyphosphate) which can be applied tothe tooth, tooth component, or inorganic dental material first and asecond composition (e.g., containing a polyamine and one or morewhitening agents) which can be applied to the tooth, tooth component, orinorganic dental material immediately after.

In some cases, a whitening adhesive containing a conjugate of at least apolyamine, a polyphosphate, and one or more whitening agents describedherein can be applied under conditions that allow a whitening agent toadhere directly or indirectly to a tooth, tooth component, or inorganicdental material to alter the appearance (e.g., color or smoothness) ofthe tooth, tooth component, or inorganic dental material. For example,an effective amount of a whitening adhesive provided herein can bedelivered to a tooth, tooth component, or inorganic dental material suchthat the appearance of the tooth, tooth component, or inorganic dentalmaterial is altered (e.g., the appearance of the tooth, tooth component,or inorganic dental material becomes whiter).

A whitening adhesive containing a conjugate of at least a polyamine, apolyphosphate, and one or more whitening agents provided herein can beapplied to a tooth, tooth component, or inorganic dental material underdry or wet conditions. In some cases, a whitening adhesive can beapplied under typical conditions found in the mouth (e.g., the presenceof saliva). For example, a whitening adhesive can be applied to a tooth,tooth component, or inorganic dental material in the presence of salivato alter the appearance of the tooth, tooth component, or inorganicdental material.

Any appropriate formulation can be used to deliver a whitening adhesivecontaining a conjugate of at least a polyamine, a polyphosphate, and oneor more whitening agents provided herein to a tooth, tooth component, orinorganic dental material. For example, a whitening adhesive providedherein can be incorporated into a toothpaste, a mouth wash, a mouthrinse, an ingestable substance such as a drink or a food product, gum(e.g., chewing gum), gels (an application gel), powders, or creams. Forexample, a whitening adhesive provided herein can be delivered on a filmstrip (e.g., a wax or plastic strip, such as a polyethylene strip) orapplied directly to a tooth, tooth component, or inorganic dentalmaterial and covered with a film strip. For example, a whiteningadhesive provided herein can be delivered in a dental tray or a mouthdam fit to a mammal's (e.g., a human's) tooth structure. In some cases,a formulation including a whitening adhesive provided herein can includeone or more pharmaceutical excipients. For example, a toothpastecontaining a whitening adhesive described herein can include one or morethickeners (e.g., cellulose derivatives, polyvinylpyrollidones, mineralcolloids, or polyethylene glycol (PEG)), buffers, surfactants,fluorides, flavorings (e.g., peppermint, spearmint, wintergreen, orbubble gum), sweeteners (e.g., sucralose or xylitol), sugar alcohols(e.g., sorbitol, glycerol, or xylitol), sensitivity reducers (e.g.,potassium nitrate), humectrants (e.g., glycerin), and/or antibacterialagents (e.g., Triclosan or zinc chloride) that do not interfere withaltering the appearance (e.g., whitening) of a tooth, tooth component,or inorganic dental material.

An effective amount of a whitening adhesive containing a conjugate of atleast a polyamine, a polyphosphate, and one or more whitening agentsprovided herein can be any appropriate amount that alters the appearanceof a tooth, tooth component, or inorganic dental material withoutinducing significant toxicity. It will be appreciated that the amountcan be higher for certain formulations, e.g., mouthwash.

In some cases, a whitening adhesive containing a conjugate of at least apolyamine, a polyphosphate, and one or more whitening agents providedherein can be applied to a tooth, tooth component, or inorganic dentalmaterial to give the tooth, tooth component, or inorganic dentalmaterial a whiter appearance, to prevent biofilms, and/or to repairenamel.

In some cases, a whitening adhesive containing a conjugate of at least apolyamine, a polyphosphate, and one or more whitening agents providedherein can be applied to a tooth, tooth component, or inorganic dentalmaterial for a period of time prior to washing, rinsing, or removal suchthat the appearance of the tooth, tooth component, or inorganic dentalmaterial is altered (e.g., the appearance of the tooth, tooth component,or inorganic dental material becomes whiter). For example, a toothpasteor other formulation configured to include a whitening adhesivecontaining a conjugate of at least a polyamine, a polyphosphate, and oneor more whitening agents as described herein can be applied (e.g.,applied directly or formed on) to a tooth, tooth component, or inorganicdental material and remain in contact with that tooth, tooth component,or inorganic dental material, without rinsing, for from about 30 secondsto about 60 minutes (e.g., from about 30 seconds to about 45 minutes,from about 30 seconds to about 30 minutes, from about 30 seconds toabout 25 minutes, from about 1 minute to about 20 minutes, from about 2minutes to about 15 minutes, from about 3 minutes to about 10 minutes,or from about 4 minutes to about 6 minutes). In some cases, such as witha mouth wash, mouth rinse, or application gel, a whitening adhesive canbe allowed to be in contact with a tooth, tooth component, or inorganicdental material for a period of time for the composition to saturate thetooth, tooth component, or inorganic dental material.

In some cases, a tooth, tooth component, or inorganic dental material(e.g., a human's tooth) can be prepared prior to applying a whiteningadhesive containing a conjugate of at least a polyamine, apolyphosphate, and one or more whitening agents provided herein. Forexample, a tooth, tooth component, or inorganic dental material can bewashed, brushed, or polished (e.g., polished with pumice) prior toapplying a whitening adhesive provided herein. In some cases, thesurface of the tooth, tooth component, or inorganic dental material canbe treated with one or more agents capable of exposing calcium phosphatebinding sites. For example, a tooth, tooth component, or inorganicdental material to be treated with a whitening adhesive provided hereincan be contacted with EDTA or phosphoric acid to expose calciumphosphate binding sites present on the tooth, tooth component, orinorganic dental material. In the case of phosphoric acid treatment,only tooth enamel can be exposed to the acid to prevent or reduce therisk of soft tissue damage.

In some cases, an assay can be performed to confirm that a whiteningadhesive containing a conjugate of at least a polyamine, apolyphosphate, and one or more whitening agents provided herein or acomponent of a composition provided herein has binding affinity for atooth, tooth component, or inorganic dental material. For example, amaterial to be tested can be incubated with a HA matrix, and the amountof material in solution after HA binding can be compared with theinitial concentration to determine, by difference, the amount of boundmaterial. See, e.g., Raj et al., J. Biol. Chem., 267:5968-5976 (1992).In some cases, the HA bound material can be directly measured afterdissolving the HA matrix with EDTA (Lamkin et al., J Dent. Res.,75:803-808 (1996)). In some cases, an assay can be performed with an HAmatrix that was pre-incubated with human saliva to coat the HA withproteins as described elsewhere (Lamkin et al., J Dent. Res., 75:803-808(1996)). In such cases, unbound saliva proteins can be removed bywashing since their presence may interfere with the polyelectrolyteconcentration determinations.

Any appropriate method can be used to assess the affinity of a whiteningadhesive containing a conjugate of at least a polyamine, apolyphosphate, and one or more whitening agents provided herein for atooth, tooth component, inorganic dental material, or an HA matrix. Forexample, bound and unbound whitening adhesive can be quantified, when afluorescent polypeptide such as BFP is used, by measuring thefluorescence of the fluorescence emitting polypeptide of thecomposition. In some cases, a whitening adhesive provided herein can beassessed for the ability to bind in vitro to a human tooth or a humantooth component. The tooth or tooth component can be subjected todifferent degrees of cleaning, such as brushing or polishing withpumice. The tooth or tooth component can then be treated with humansaliva to form the acquired dental pellicle and incubated with awhitening adhesive provided herein in the presence and absence ofsaliva. The binding to the tooth or tooth component can be determined bymeasuring the degree of whiteness.

Any appropriate method can be used to assess a whitening adhesivecontaining a conjugate of at least a polyamine, a polyphosphate, and oneor more whitening agents provided herein for the ability to alter theappearance of a tooth, tooth component, or inorganic dental material.For example, visual inspection techniques can be used to determinewhether or not a whitening adhesive provided herein can alter theappearance of a tooth, tooth component, or inorganic dental material.Such visual inspection techniques can include using shade guides forcomparison as described elsewhere (Paravina et al., J. Esthet. RestorDent., 19:276-283 (2007)). In some cases, the ability of a whiteningadhesive provided herein to alter the appearance of a tooth, toothcomponent, or inorganic dental material (e.g., to make a tooth, toothcomponent, or inorganic dental material appear whiter) can be measuredusing reflectance spectrophotometry. In such cases, the tooth, toothcomponent, or inorganic dental material can be illuminated with a whitelight source and analyzed as to the amount of light absorbed atdifferent wavelengths by reflectance spectrophotometry (colorimetry).These measurements can then be repeated with the UV light filtered fromthe light source. The difference in the reflectance values obtained withthe inclusion and exclusion of UV light is the UV fluorescence spectrumof the tooth surface (see, e.g., Park et al., Dental Materials,23:731-735 (2007)).

A whitening adhesive containing a conjugate of at least a polyamine, apolyphosphate, and one or more whitening agents (e.g., TiO₂ and/or ZnO)provided herein can lack dyes, which can potentially have toxicproperties.

The invention will be further described in the following examples, whichdo not limit the scope of the invention described in the claims.

EXAMPLES Example 1: Preparation of Polyelectrolyte Adhesive WhiteningSolution or Gel

To prepare a whitening adhesive, 1 wt % whitening agent (e.g., titaniumdioxide and/or zinc oxide optionally containing hydroxyapatite, bluefluorescent protein, silicon dioxide, bioactive glass or others) wasadded to water and/or a thickening agent (e.g., polyvinylpyrrolidone,such as Kollidon K90F, or Cellulose Gum) containing the tooth specimensincubated for 5 minutes, followed by addition of 5 wt % polymer (e.g.,PAA, PAS-92, or PAA-D41 adjusted to pH 7 to 9). A 5 wt % phosphatereagent (e.g., STP, SHMP, TPP, PP) was added, and the mixture wasincubated for 30 minutes, followed by rinsing with water and brushingfor 10 seconds with an electric toothbrush. A picture depicting thescheme of this preparation method is shown in FIG. 3A.

The compositions of the polyelectrolyte mixtures are shown in Table 1.

TABLE 1 Stock Conc. Amount Added Final Conc. Reagent (%) (mL) (Cf, Wt %)water/Thickening 1 10 0.446 agent TiO2 1 1 0.045 STP 5.7 1.4 0.356Polymer 2.5 10 1.116 Total 22.4

FIG. 4 contains photographs showing the appearance of whiter teethfollowing application of an exemplary whitening adhesive containingpolyallylamine (PAA), sodium trimetaphosphate (STP), and titaniumdioxide (TiO₂) (top panel) or an exemplary whitening adhesive containingPAS-92, STP, and TiO₂ (bottom panel).

Example 2: Polyelectrolyte Adhesive with a Whitening Agent on a ToothComponent

Preparations of polyelectrolyte whitening adhesives containing eitherPAA, STP, and TiO₂; PAS-92, STP, and TiO₂; or PAA-D41, STP, and TiO₂were prepared as described below.

To prepare a whitening adhesive, 1 wt % whitening agent (e.g., titaniumdioxide and/or zinc oxide optionally containing hydroxyapatite, bluefluorescent protein, silicon dioxide, bioactive glass or others) wasadded to a solution of 14 wt % polymer (e.g., PAA, PAS-92, or PAA-D41adjusted to a pH between 7 and 9), such that the whitening agentconcentration was 0.2 wt % and polymer was 0.75 wt % in a tube labelledas “A”. A 25 wt % phosphate reagent (e.g., STP, SHMP, TPP, PP) wasadded, to a tube labelled “B” containing H₂O (or thickening agent) suchthat the concentration of phosphate reagent was 5.0 wt % and H₂O (orthickening agent) was 0.55 wt % of stock.

Whitening adhesives were applied to bovine tooth specimens previouslystained with tea and coffee concentrates in sequential order (tube-Afollowed by tube-B, as depicted in FIG. 3B), and the mixture wasincubated for 30 minutes, followed by rinsing with water and brushingfor 10 seconds with an electric toothbrush.

The compositions of the polyelectrolyte mixtures are shown in Table 2.

TABLE 2 Final Conc. Reagent Stock Conc. Amount Added (wt %)water/thickener  X% 41 uL .055X TiO2  1% 15 uL 0.20 STP 25% 15 uL 5.0Polymer 14%  4 uL 0.75 Total 75 uL

As shown in FIG. 5, after application of a whitening adhesive containingPAA, STP, and TiO₂ the teeth appeared whiter, even after brushing.

Example 3: Polyelectrolyte Adhesive with TiO₂

Preparations of polyelectrolyte whitening adhesives containing PAA, STP,and TiO₂ were prepared as described below.

To prepare a whitening adhesive, 1 wt % TiO₂ was added to a solution of14 wt % PAA adjusted to about pH 8, such that the whitening agentconcentration was 0.2 wt % and polymer was 0.75 wt % in a tube labeledas “A”. A 25 wt % phosphate reagent (e.g., STP) was added, to a tubelabeled “B” containing H₂O such that the concentration of STP reagentwas 5.0 wt % and H₂O was 0.55 wt % of stock.

Whitening adhesives were applied to bovine tooth specimens, previouslystained with tea and coffee concentrates, in sequential order (tube-Afollowed by tube-B as depicted in FIG. 3B) and the mixture was incubatedfor 30 minutes, followed by rinsing with water and brushing for 10seconds with an electric toothbrush.

As shown in FIG. 5, after application of a whitening adhesive containingPAA, STP, and TiO₂, the teeth appeared whiter, even after brushing

Example 4: Polyelectrolyte Adhesive with TiO₂ and HA

Preparations of polyelectrolyte whitening adhesives containing PAA, STP,and a combination of TiO₂ and HA were prepared as described below.

To prepare a whitening adhesive, 1 wt % TiO₂ and 5 wt % HA was added toa solution of 14 wt % PAA adjusted to about pH 8, such that the TiO₂concentration was 0.1 wt %, HA concentration was 0.5 wt %, and polymerwas 0.75 wt % in a tube labeled as “A”. A 25 wt % phosphate reagent(e.g., STP) was added, to a tube labeled “B” containing H₂O such thatthe concentration of STP reagent was 5.0 wt % and H₂O was 0.55 wt % ofstock.

Whitening adhesives were applied to bovine tooth specimens, previouslystained with tea and coffee concentrates, in sequential order (tube-Afollowed by tube-B as depicted in FIG. 3B) and the mixture was incubatedfor 30 minutes, followed by rinsing with water and brushing for 10seconds with an electric toothbrush.

As shown in FIG. 6, after application of a whitening adhesive containingPAA, STP, TiO₂, and HA, the teeth appeared whiter, even after brushing.

Example 5: Polyelectrolyte Adhesive with TiO₂ and BFP

Preparations of polyelectrolyte whitening adhesives containing PAA, STP,and a combination of TiO₂ and BFP were prepared as described below.

To prepare a whitening adhesive, 1 wt % TiO₂ and 5 wt % BFP was added toa solution of 14% PAA adjusted to about pH 8, such that the TiO₂concentration was 0.1 wt %, BFP concentration was 0.5 wt %, and polymerwas 0.75 wt % in a tube labeled as “A”. A 25 wt % phosphate reagent(e.g., STP) was added, to a tube labeled “B” containing H₂O such thatthe concentration of STP reagent was 5.0 wt % and H₂O was 0.55 wt % ofstock.

Whitening adhesives were applied to bovine tooth specimens, previouslystained with tea and coffee concentrates, in sequential order (tube-Afollowed by tube-B as depicted in FIG. 3B) and the mixture was incubatedfor 30 minutes, followed by rinsing with water and brushing for 10seconds with an electric toothbrush.

As shown in FIG. 7, after application of a whitening adhesive containingPAA, STP, TiO₂, and BFP, the teeth appeared whiter, even after brushing.

Example 6: Polyelectrolyte Adhesive with TiO₂ and ZnO

Preparations of polyelectrolyte whitening adhesives containing PAA, STP,and a combination of TiO₂ and ZnO were prepared as described below.

To prepare a whitening adhesive, 1 wt % TiO₂ and 5 wt % ZnO was added toa solution of 14% PAA adjusted to about pH 8, such that the TiO₂concentration was 0.1 wt %, ZnO concentration was 0.5 wt %, and polymerwas 0.75 wt % in a tube labeled as “A”. A 25 wt % phosphate reagent(e.g., STP) was added, to a tube labeled “B” containing H₂O such thatthe concentration of STP reagent was 5.0 wt % and H₂O was 0.55 wt % ofstock.

Whitening adhesives were applied to bovine tooth specimens, previouslystained with tea and coffee concentrates, in sequential order (tube-Afollowed by tube-B as depicted in FIG. 3B) and the mixture was incubatedfor 30 minutes, followed by rinsing with water and brushing for 10seconds with an electric toothbrush.

As shown in FIG. 8 (top panel), after application of a whiteningadhesive containing PAA, STP, TiO₂, and ZnO, the teeth appeared whiter,even after brushing.

Example 7: Polyelectrolyte Adhesive with ZnO

Preparations of polyelectrolyte whitening adhesives containing PAA, STP,and ZnO were prepared as described below.

To prepare a whitening adhesive, 5 wt % ZnO was added to a solution of14 wt % PAA adjusted to about pH 8, such that the ZnO concentration was1 wt %, and polymer was 0.75 wt % in a tube labeled as “A”. A 25 wt %phosphate reagent (e.g., STP) was added, to a tube labeled “B”containing H₂O such that the concentration of STP reagent was 5.0 wt %and H₂O was 0.55 wt % of stock.

Whitening adhesives were applied to bovine tooth specimens, previouslystained with tea and coffee concentrates, in sequential order (tube-Afollowed by tube-B as depicted in FIG. 3B) and the mixture was incubatedfor 30 minutes, followed by rinsing with water and brushing for 10seconds with an electric toothbrush.

As shown in FIG. 8 (bottom Panel), after application of a whiteningadhesive containing PAA, STP, and ZnO, the teeth appeared whiter, evenafter brushing.

Example 8: Polyelectrolyte Adhesive with STP or SHMP or PP or TPP

To prepare a whitening adhesive, 1 wt % whitening agent (e.g., titaniumdioxide and/or zinc oxide optionally containing hydroxyapatite, bluefluorescent protein, silicon dioxide, bioactive glass or others) wasadded to water and/or a thickening agent (e.g., polyvinylpyrrolidonesuch as Kollidon K90F, Cellulose Gum) containing the tooth specimensincubated for 5 minutes, followed by addition of 20 wt % polymer (e.g.,PAA, PAS-92, PAA-D41 adjusted to pH 7 to 9). A 25 wt % phosphate reagent(e.g., STP, SHMP, TPP, PP) was added, and the mixture was incubated for30 minutes, followed by rinsing with water and brushing for 10 secondswith an electric toothbrush. A picture depicting the scheme of thispreparation method is shown in FIG. 3A.

The composition of the polyelectrolyte mixture is shown in Table 3.

TABLE 3 Stock Conc. Amount Added Final Conc. Reagent (%) (mL) (Cf, Wt %)water/Thickening 1 9.25 0.740 agent/1x PBS TiO2 1 1 0.080 STP or SHMP or25 1 2.000 PP or TPP Polymer 20 1.25 2.000 Total 12.5

As shown in FIGS. 9A and 9B, after application of a whitening adhesiveobtained using various polyanions (or phosphate reagents like STP orSHMP or TPP or PP) with PAA, and TiO₂, the teeth appeared whiter, evenafter brushing to various degree (FIG. 9A) and the same was true whenperformed with polymer PAS-92 (FIG. 9B).

Other Embodiments

It is to be understood that while the disclosure has been described inconjunction with the detailed description thereof, the foregoingdescription is intended to illustrate and not limit the scope of thedisclosure, which is defined by the scope of the appended claims. Otheraspects, advantages, and modifications are within the scope of thefollowing claims.

1. (canceled)
 2. A method for altering an appearance of teeth, whereinsaid method comprises applying polyallylamine, a polyphosphate, and awhitening agent to teeth, wherein said applying step alters saidappearance of said teeth, and wherein said polyallylamine comprises:


3. The method of claim 2, wherein said polyphosphate is selected fromthe group consisting of sodium hexametaphosphate, sodiumtrimetaphosphate, sodium tripolyphosphate, and sodium pyrophosphate. 4.The method of claim 2, wherein said polyphosphate is a cyclicpolyphosphate, a linear polyphosphate, a potassium salt of apolyphosphate, or a sodium phosphate salt of a polyphosphate.
 5. Themethod of claim 2, wherein said polyphosphate is a potassium salt of apolyphosphate.
 6. The method of claim 2, wherein said polyphosphate is asodium phosphate salt of a polyphosphate.
 7. The method of claim 2,wherein said whitening agent comprises at least one of titanium dioxide,hydroxyapatite, silicon dioxide, zinc oxide, bioactive glass, and bluefluorescent protein.
 8. The method of claim 2, wherein said whiteningagent is titanium dioxide.
 9. The method of claim 2, wherein saidwhitening agent is silicon dioxide.
 10. The method of claim 2, whereinsaid whitening agent is zinc oxide.